Certain amine-modified thermoplastic phenol-aldehyde resin salts and method of making same



CERTAIN AMINE-MODIFIED THERMOPLASTIC PHENOL-ALDEHY DE RESIN SALTS AND METH- OD OF MAKING SAME Melvin De Groote, St. Louis, Corporation, Wilmington, ware Mo., assignor to Petrolite Del., a corporation of Bela- No Drawing. Original application January 2, 1953, Serial No. 329,483. Divided and this application April 9, 1956, Serial No. 576,818

8 Claims. (Cl. 260--53) The present invention is a continuation-in-part of my two copending applications, Serial No. 288,743, filed May 19, 1952, now abandoned, and Serial No. 296,084, filed lane 27, 1952, now U. S. Patent 2,679,485, and a division of my eopending application Serial No. 329,483, filed January 2, 1953, now Patent No. 2,771,441.

My invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. My invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in dernulsification.

My aforementioned copending application, Serial No. 288,743, filed May 19, 1952, is concerned with the process of condensing certain phenol-aldehyde resins, therein described in detail, with certain basic hydroxylated secondary monoarnines, also therein described in detail, and formaldehyde.

The present invention is concerned with the aforementioned amino resin condensates in the form of a gluconic acid salt, i. e., a form in which all or part of the basic nitrogen atoms are neutralized with gluconic acid, i. e., converted into the salt of gluconic acid.

My aforementioned copending application, Serial No. 296,084, filed June 27, 1952, is concerned with a process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of the certain amine resin condensates described'in my aforementioned application Serial No. 288,743.

As far as the use of the herein described products go for purpose of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have sufficient hydrophile character to meet at least the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity. v

The present invention involves the surface-activity of the gluconic acid salts, i. e., either where only one basic amino nitrogen atom is neutralized or where all or part of the basic amino nitrogen atoms are neutralized. Such gluconic acid salts may not necessarily be xylene-soluble. if such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a wat r-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weightof xylene, followed by addition of water. Such test is obviously: the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the 2,839,498 Patented June 17, 1958 reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious varient.

For convenience, what is said hereinafter will be divided into seven parts:

Part 1 is concerned with the general structure of the amine-modified resins which are converted into the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with appropriate basic secondary,

hydroxylated amines which may be employed in the preparation of the herein described amine-modified resins;

Part 4 is concerned with the reactions involving the resin, the amine, and formaldehyde to produce the specifie products or compounds which are neutralized subsequently with gluconic acid; and

Part 5 is concerned with the conversion of the basic condensate into the corresponding salt of gluconic acid;

Part 6 is concerned with the resolution of petroleum emulsion of the water-in oil type by means of the pre: viously described chemical compounds or reaction products in the form of gluconic acid salts; and

Part 7 is concerned with uses for the product herein described, either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the Water-in-oil type. This part is limited also to the use of the gluconic acid salts.

For reasons which are obvious particularly for convenient and ease of comparison, Parts 1, 2, Sand 4 are in substantially verbatim form as they appear in the two aforementioned copending applications, Serial Nos. 288,- 743, and 296,084, and particularly as they appear in the latter.

PART 1 The compounds herein described and particularly use I ful as dernulsifying agents are gluconic acid salts of heat-.

stable oxyalkylation-susceptible resinous condensation.

R\ H OH H I- OH 1 OH H /R" N-C- -o- -o -o-N H H H H R R v R R R in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and n generally is a small whole number varying from 1 to 4.

In the resin structure it is shown as being derived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from a basic amine, and usually a strongly basic amine, and may be indicated thus:

in which R represents any appropriate hydrocarbon radi cal such as an alkyl, alicyclic, arylalkyl radical, etc., with the proviso that at least one of the radicals designated by R has at least one hydroxyl radical. The hydro- Such formulaessence carbon radical may have the carbon atom chain or equivalent interrupted by oxygen atoms. The only limitation is that the radical should not have a negative radical which considerably reduces the basicity of the amine, such as an aryl radical or an acyl radical. The introduction of two such amino radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the resultant product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; the second place, depending on the size of the radical R, there may be a counter-balancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. The presence of onev or more hydroxyl radicals introduces a significant hydrophile effect. Finally, in such cases where R contains one or more oxygen atoms in the form of an ether linkage another effect is introduced, particularly another hydrophile effect.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the orthoor para position, i. e., the phenols themselves are difunctional phenols.

Theresins herein employed contain only two terminal groupswhich are; reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylol-forming reactions. As is well known, although one may start with difunctional phenols, and depending on the procedure employed, one may obtain cross-linking which indieates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resinformation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta position. For instance, in the case of phenolaldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

The resins herein employed are soluble in a nonoxygenated hydrocarbon solvent, such as benzene or xylene.

The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin molecule.

The condensation products. here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is heat stable and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxycthylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above 100 C. without becoming an insoluble mass.

Although these condensation products have been prepared primarily with the thought in mind that they are precursors for subsequent reaction, yet as such and without further reaction, they have definitely valuable properties'and uses as hereinafter pointed out.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperatures going up to 140 to 150 C.

What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 50 C., yet the reaction. does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process is not intended to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added-many order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine so as to introduce a methylol group attached to'nitrogenwhich, in turn, would react with the resin molesule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of forrna1- dehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

PART 2 It is well known that one can readily purchase on the open market, or prepare fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula In the above formula, 11 represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the totalnumber of phenol nuclei varies from 3 to 6, i. e., It varies frornl to 4; R represents. an aliphatic hydrocarbon substituent, generally an alykyl radical having'from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decylor dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

The resinsherein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or Xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in. U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic non-hydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde or only one mole of the amine may combine with the resin molecule, or even to a very slight extent if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As hasbeen pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemin which R is the divalent radical obtained fromthe particular aldehyde. employed to form the resin. for reasons which are obvious the condensation product obtained appears to be described best of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See pre viously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized.

in terms of the method Similarly, if a strong base is. used as a catalyst it is preferable that thebase be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few l0ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case it to have the resin neutral.

In preparing resins one does not get a single polymer, 9 i. e., one having just'3 units, or just 4 units, or just 5 units, or just 6 units, etc. (It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus; the molecular weight may be such that it'corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of 'the resins I found no reasonfor using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the followi'ng table:

TABLE 1 Mol. wt. Ex- 1 Position 1 R of resin ample R of R derived n molecule number fr0m- (based 1 on n+2) 2a Tertiary butyl Para Formal- 3. 5 882. 5

3a Secondary butyl. 3. 5 852. 5 5a Tertiary amyl 3. 5 959. 5 6a Mixed secondary 3. 5 S05. 5

i and tertiary amyl. 7a 3. 5 805.5 3. 5 1,036. 5 3. 5 l, 190. 5 3. 5 1, 267. 5 3. 5 1, 344. 5 3. 5 1, 49s. 5 3. 5 945. 5

3. 5 1, 1-18. 5 3. 5 l, 456. 5 a. 5 1, 00s. 5

3. 5 1,085. a 5 1, s93. Tertiary butyl 4. 2 996. Tertiary ethyl"... 4. 2 1, 083. N n 4. 2 1,430. 4. 8 1,094. .4. s 1,1ss. 4. 8 1, 570. 1. 5 604. l. 5 653. 1. 6 688.

.do.....- do 2.0 692. ..do. ..do 2.0 748.

PART 3 As has been pointed out previously the amine herein employed as a reactant is a basic hydroxylated secondary monoamine whose composition is indicated thus:

have at least one bydroxyl radical. A large number of.

QC DUO coo ease ents-m 61011::

7 secondary amines are available and may be suitably employed as reactants for the present purpose. Among others, one may employ diethanolamine, methyl ethanolamine, dipropanolamine and ethylpropanolamine. Other suitable secondary amines are obtained, of course, by taking any suitable primary amine, such as an alkylamine, an arylalk-ylamine, or an alicyclic amine, and treating the amine with one mole of an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycide, or methylglycide. Suitable primary amines which can be so converted into secondary amines, include butylamine, amylamine, hexylamine, higher molecular weight amines derived from fatty acids, cyclohexylamin e, benzylamine, furfurylamine, etc. In other instances. secondary amines which have at least one hydroxyl radical can be treated similarly withan oxyalkylating agent, or, for that matter, with an alkylating agent such as benzylchloride, esters ofchloroacetic acid, alkyl bromides, dirnethylsulfate, esters of sulfonic acid, etc., .so as to convert the primary amine into a secondary amine. Among others, such amines include 2-amino-1-butanol, 2 -amino- Z-methyl-l-propanol, 2 amino-Z-methyl-1,3-propanediol, Z-amino-Z-ethyl-1,3-propanediol, and tris-(hydroxymethyl)-aminornethane. Another example of such amines is illustrated by 4-amino-4-methyl-2-pentanol.

Similarly; one can prepare suitable secondary amines which have not only ahydroxyl group but also one or more divalent oxygen linkages as part of an ether radical. The preparation of such amines or suitable reactants for preparing them'has been described in the literature and particularly'in two United States patents, to wit, U. S. Patents Nos. 2,325,514, dated July 27, 1943, to Hester, and 2,355,337, dated August 8, 1944, to Spence. The latter patent describes typical haloalkyl ethers such as CHaOCzEhCl CHr-CH: (3H2 CH-CH2OC2H40C2HB1 zHaOCz 4 2 4 C2H4 G2H4Cl Such haloalkyl-ethers can reacted with ammonia or with a primary amine, such as ethanolamine, propanolamine, monoglycerylamine, etc., to produce a secondary amine in which there is not only present a hydroxyl radical but a repetitious ether linkage. Compounds can be readily obtained which are exemplified by the following formulas:

' otnsooimoczm) .rroo zui (c ufl oczniociniocim) \NH noogrn orngooniomonomeno011cm) \NH Hooini (CH3OOH7CH2OOHzGHzOCHzCH2) Nn uo'oirn onaoonzcnzoniontonzoni) NH nooini or comparable compounds having two hydroxylated groups of dififerentlengths as in noonzonzoornonaoonzoni) V NH 'HOO2H/ identified previously as Example 2a. I 76 2,839,498 I v H 8 Other examples of suitable amines include alpha-methylbenzylamine and monoethanolamine; also amines obtainedby treating cyclohexylmethylamine with one mole of an oxyalkylating' agent as previously describedgbetaethylhexyl-butanolamine, diglycerylamine, etc. Another type of amine which is of particular interest because it includes a very definite hydrophile group includes sugar amines such as .glucamine, gelactamine and fructamine, such as N hydroxyethylglucarnine, N hydroxyethylalactamine, and N hydroxyethylfructamine.

Other suitable amines may be illustrated by.

$113 HO.CH2-?.CH1OH i s nocnlccuion CH3 CH C XCIHOH r rn CHallilHzOH I CH See, also, corresponding hydroxylated amines which can be obtained from rosin or similar raw materials and described in U. S. Patent No. 2,510,063, dated June 6, 1950, to Bried. Still other examples are illustrated by treatment of certain secondary amines, such as the following, with .a mole of an oxyalkylating agent as described;

phenoxyethylamine, phenoxypropylamine, phenoxyalphe- PART 4 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process.

itself. The condensation of the resin, the amine and formaldehyde is described in detail in applications Serial Nos. 288,743 and 296,084, and reference is made to those applications for a discussion of the factors involved.

Little more need be said as to the actualprocedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration: i 7 V Example '15 The phenol-aldehyde resin is the one that has been It was obtained from a para-tertiary butylphenol and formaldehyde. The

completely neutralized at the end of the reaction. The.

molecular weight of the resin was 882.5. This corresponded to an averageof about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding were powdered and mixed with 700 grams of xylene. The mixture was refluxed until solution was complete. It was then adjusted to approximately 30 to 35 C. and 210 grams of diethanolamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde used was a 37% solution and 160 grams were employed which were added in about 3 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C. for about 21 hours. At the end of this period of time it was refluxed, using a phaseseparating trap and a small amount of aqueous distillate withdrawn from time to time and the presence of unreacted formaldehyde noted. Any unreacted formaldehyde seemed to disappear within approximately 3 hours after the refluxing was started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached about '10 150 C. The mass was kept at this higher temperature for about 3% hours and reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or a tacky resin. The overall reaction time was a little over hours. In other instances it has varied from approximately 24 to 36 hours. The time can be reduced by cutting the low temperature period to about 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the Water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

TABLE II Strength of Reac- Reac- Max. Ex. Resin Amt, formal- Solvent used tion tion dts- N 0. used grs. Amine used and amount dehyde and amt. temp, time, till.

soln. and 0. (hrs.) temp,

amt. 0.

882 Diethanolamine, g 37%, 162 g Xylene, 700 gm. 22-26 32 137 480 Diethanolamlne, g 81 Xylene, 450 g 21-23 28 150 633 do do..- Xylene, 600 g 20-22 36 441 Dipropanolamine, 133 g. 30%, 100 g... Xylene, 400 15.... 20-23 34 146 480 do do Xylene, 450 g 21-23 24 141 633 do do. Xylene, 600 g 21-28 24 145 882 Ethylethanolamine, 178 g 37%, 162 g.-. Xylene, 700 g.... 20-26 24 152 480 Ethylethanolamine, 89 g 37%, 81 g Xylene, 450 gm. 24-30 28 151 633 do do Xylene, 600 g.... 22-25 27 147 473 Oyclohexylethanolamtne, 143 Xylene, 450 g 21-31 31 146 511 d d0. 22-23 36 148 665 do Xylene, 550 g..- 20-24 27 152 OzH5OCzH OC2H4 13b 2a 441 NH, 176 g do Xylene, 400 g-... 21-25 24 HOOBH" CzHs OC2H4OC2H4 140" 5a..--- 480 i NH, 176 g do-.-. Xylene, 450 g 20-26 26 146 HOC2H O2HsOC2H1OOzH4 150---. 9a.-. 595 L NH, 176 g do Xylene, 550 g 21-27 so 147 HOC2H4OC2H0C2H4 16b 2a.-- 441 NH, 192 g do Xylene, 400 g.... 20-22 30 148 HOCQHJOCEHAOC2HI 17b 5a..... 480 NH, 192 g do do 20-25 28 150 HOOZHI HOQzH4O02H40C2H4 181).. 1411.. 511 NH, 192 g -.dO Xylene, 500 gnu 21-24 32 149 HooiH.

HOC2H4OC2H4OC2H4 191)-. 2201.-.- 498 NH, 192 g ...---d0 Xylene, 450 g 22-25 32 153 HOG2H TABLE II-Continued Strength of Reac- Reac- Max. Ex. Resin Amt., Amine used and amount formalde- ,7 Solvent used tion, tlon distill. No. used grs. hydesoln. and amt. temp, time, temp,

and amt. 0. (hrs.) C.

CH3(OC2H4)3 b 23s.... 542 'NH, 206 g 30%, 100 g Xylene, 500 gm. 21-23 36 151 HOCZH4 OH3(OOzII4)3 21IJ 25m-.- 547 NH, 206 g do do 25-30 34 148 CH (OC2H4)3 22b- 2a. 441 NH, 2065: do Xylene, 400 g.. 22-23' 31 146 3002 3 236.". 26a 595 Deeylethanolamine, 201 g 37%, 81 g. Xylene, 500 g 22-27 24 145 2412---. 27a 391 Deoylethanolamine, 100g 30%, 50 g... Xylene, 300 g 21-25 26 147 PART 5 The conversion of the basic condensates of the kind previously described into the corresponding salt of gluconic acid is a simple operation since it is nothing more nor less than neutralization. The condensates invariably contain more than two basic nitrogen atoms. One can neutralize eitherfone, or both, basic'nitrogen atoms.

Gluconic acid is available as a 50% solution. Dehydration causes decomposition. This is not true of the salts, at least not of the salts of the herein described condensates. Such salts appear to be stable, or stable for all practical purposes, at temperatures slightly above the boiling point of water and perhaps'at temperatures as high as 150 C. or there'abouts.

For reasons pointed out previously, it is most convenient to handle the condensate as a solution, generally .a solution in an inexpensive solvent, such as benzene,

xylene, an aromatic petroleum solvent, or the like. A

number of the condensates previously described 'have been prepared in solution as noted. Adding thec'alculated stoichiometric amount of 50% gluconic acid, calculated on the basis of the theoretical basic nitrogen perhaps slightly on the acid side. merely a matter of agitating at room temperature, or somewhat higher temperature if desired, particularly under a reflux condenser. After salt formation is complete, l have permitted the solution to stand for about 6 to 72 hours. Sometimes, depending on the composition, there is some separation of an aqueous phase. 'On a laboratory scale, this procedure is conducted in a separatory funnel. If there is separation of an aqueous phase, the aqueous phase is discarded and the solution can be brought back 'to a predetermined concentration by the addition of a hydrocarbon solvent, such as xylene, or by the addition of an alcohol, such methyl, ethyl, or propyl alcohol; or, if need be, one can employ a bridge solvent having hydrotropic properties in case of the dicthylether of ethyleneglycol, or similar solvents.

The gluconic salts can be obtained in non-aqueous solution by using a slightly modified procedure. The

procedure depends on'the fact that the phase-separating trap can be used but it is preferable to stay below 150 C. so as to avoid any possible decomposition.

The salt formation is i The xylene solution of the condensate, as previously W described, is subjected to vacuum distillation so as to remove about one-half the xylene. Approximately twothirds of the xylene removed is replaced by benzene.

This mixed solvent combination is subjected to refluxing H action under a condenser with a phase-separating trap. With the distillation point adjusted so as to be somewhere between 11 to C. the mixture is refluxed and the water separated. If it is not within this range more benzene is added or, if need be, a little more xylene is added to bring it within the range. By this method the p'lraseseparating trap eliminates the water. The temperature at all times ,is left below C. At the end of the separation a suitable amount of solvent is added, or eliminated, by distillation so as to yield a solution of predetermined concentration, for instance, 50%.

Using a somewhat similar procedure one can obtain the solvent-free material by merely subjecting the xylene solution of the condensate to vacuum distillation so as to remove all the xylene. The condensate itself is perfectly stable at C. or thereabouts and, thus there is no particular danger of degradation involved in this step. The solvent-free material is then dissolved in benzene instead of xylene and water eliminated in the manner previously described. The benzene is eliminated by vacuum distillation in such a Way that the temperature never gets above 135 C. or 140 C. Actually, with care the solution previously described, to wit, the xylenebenzene solution, also .can be removed Without decomposition.

Broadly speaking, the gluconic acid salts represent salts of hydroxylated tertiary amines. In other words, there is an. analogy .to trieth'anolamine oleate or,forthat matter, triethanolamine gluconate, If triethanolamine gluconate is heated to approximately 150 C., there seems to be evidence there is a slow conversion into the acylated amine, i. e., gluconyl triethanolamine, comparable to the conversion of triethanolamine oleate into oleyl triethanolamine. For this reason, previous reference to decomposition must be construed to mean not only decomposition in the sense that degradation or inner others may be formed, but also in the sense that an entirely new and valuable compound may be formed. Such reaction, of course, forms water as a byproduct.

Example 10 This salt was made from condensate Example 1b. Example 1b in turn was made from resin 2a and diethanolamine. 882 grams of the resin dissolved in an equal weight of xylene were reacted with 210 grams of dicthanolamine, and 162 grams of 37% formaldehyde.

' All this has been described previously. The Weight of the condensate on a solvent-free basis was 1116 grams. This represented approximately 27 grams of basic nitrogen. To this mixture, with constant stirring, there was added 756 grams of 50% gluconic acid. The solution was poured into a separatory funnel or syphon arrangement and allowed to stand at 40 C. for about 2 /2 days. There was no aqueous separation at the bottom or, at the most, merely a trace. The solution was somewhat turbid and for this reason about 100 .grams of isopropyl alcohol were added and enough xylene to bring the final weight to just short of 3000 grams, or, more exactly 2988 grams. This represented approximately a 50% solution.

A number of other examples are included in Table III, following.

Gluconic acid salt, for example, the product of Ex ample 1c, 20%; I

A cyclohexylamine salt of a polypropylated napthalene' monosulfonic acid, 24%;

TAB LE III Condensate in turn derived from Salt formation Salt Salt from Wt. of Final ex. con- Amt. 37% conden- Theo. 50% wt. ad- No. (len- Resin Amt. sol- Amine rmsate on basic gluusted to sate No. resin. Solvent vent, Amine used used, aldesolventnitroconic approx N 0. gms. gms. gnis. hyde, tree gen, acid, 50% salt, gms. basis, I gms. gins. 50% solv.,

gms. gins,

882 Diethanolamine 210 162 1, 116 27. 756 2, 988 480 do 105 81 597 13. 378 l, 572 105 81 750 13. 5 378 1, 878 133 1 100 586 13. 6 380 1, 552 133 1 100 625 13. 6 380 l, 630 133 1 100 778 13. 6 380 1, 936 178 162 1, 084 28. 0 784 2, 952 89 81 581 14, 0 392 1, 554 633 l0 89 81 734 14. 0 392 1, 860 473 Cyclobexylethanol amine. 143 1 100 671 14.0 392 1, 734 511 do 143 81 728 14. 0 392 1, 848 665 do 143 81 882 14. 0 392 2, 150 882 Dlethanolaniine 210 162 l, 116 27. 0 378 2, 610 441 Dipropanolamine. 133 1 100 586 13. 5 189 1, 361 882 Ethylethanolamin 178 162 l, 084 28. 0 392 2, 560

1 formaldehyde.

PART 6 acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alco hol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsii'ying agent of my process may be admixed with one or more of the solvents customarily used in con-- nection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland Water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concen trations. This same fact is true in regard to the material or materials of my invention when employed as demulsifying agents.

The materials of my invention, when employed as treating or demulsifying agents, are used in the conventional way, Well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-holedemulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

An ammonium salt of a polypropylated napthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble tonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

PART 7 The gluconic acid salts herein described can .be used as emulsifying agents for oils, fats, and waxes; as ingredients in insecticide compositions; or as detergents and wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They also can be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes. Also, the gluconic acid salts are useful in dry cleaners soaps. 7 it Also, they may be used as additives in connection with other emulsifying agents; they may be employed to contribute hydrotropioettects; they may be used as antistrippers in connection with asphalts; they may beused to prevent corrosion, particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas, and also in refineries where crude oil is converted into various commercial products. The products may be used industrially to inhibit or stop microorganic growth or other objectionable lower forms of life, such as the growth of algae, or the like; they may be used to inhibit the growth of bacteria, molds, etc. They are valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils, and also to hydraulic brake fluids of the aqueous or nonaqueous type; some have definite anti-corrosive action. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters.

mahogany petroleum sul- Previous reference has been made to the fact that the gluconic acid salt previously described can be considered as a precursor in the manufacture of the corresponding ester by mere elimination of water. This is comparable, as has been pointed out, to the formation of oleyl triethanolamine from triethanolamine oleate. Such esters arevaluable for all the various purposes described immediately preceding, and particularly for the resolution of 15 petroleum emulsions of the water-in-oil type, the resolution'of petroleum emulsions of the oil-in-water type, for the prevention of corrosion of ferrous metals, and as an asphalt additive for anti-stripping purposes. Once the ester has been formed, it can be reacted again with an acid in the same manner that oley} triethanolamine can be converted into a salt. Indeed, the salts obtained by combination 'with an oil-soluble petroleum acid, i. e., mahogany acids, are particularly valuable for the prevention of corrosion.

Previous reference has been made to oxyalkylation, and particularly oxyethylation and oxypropylation. The condensate prior to conversion into a salt is .oxyalkylationsusceptible. Gluconic acid includes as part of its structure hydroxyl groups which are oxyalkylation-susceptible. Thus, it follows that the salt of the condensate contains one or more groups, indeed a plurality of groups in which a labile hydrogen atom appears, and thus are in turn, oxyalkylation-susceptible. However, it is usually diflicult, indeed extremely diflicult at times, to oxyalkylate in presence of a radical which is'in essence a salt as in the present case. economical to convert the condensate into an oxyalkylated derivative and then convert the oxyalkylated derivative into a salt of gluconic acid. Such type of compound, or cogeneric mixture, is not within the scope of the present invention.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

l. A two-step manufacturing process including the method of condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-aldehyde resin having an average molecular weightcorresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction l'between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the ,2, 4, 6 position; (b) a basic hydroxylated secondary .monoamine having not more than 32 carbon atomszin any group attachedto the amino nitrogen atom, and' formaldehyde; said condensation reaction beingconducted at .a temperature su'tficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which ,each of the three reactants have contributed part of the ultimate molecule by virtue of .a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin-molecule; and with the further proviso that the resinous condensation product resulting from the process be heat-stable andfollowed by neutralizationwith gluconic acid. r

2. A two-step manufacturing process including the method of condensing (a) an oxyalkylation-susceptible, fusible, no-nsoxygenated organic solvcnt-soluble, waterinsoluble, low-stagephenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolicnuclei per resin molecule; said resin being difunctional only'in regard to methylol-forming reactivity; said resin being derivedby reaction between a difunctional monoh ydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol;

For this reason it .is more practical and more said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula water and below the pyrolytic point of the reactants and rcsultants of reaction; with the proviso that the condensa- 7 tion reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehydoderived methylene bridge connecting the amino nitrogen atom with a resin molecule;

with the further proviso that the molar ratio of reactants be approximately I, 2 and 2 respectively; and with the final proviso that the resinous condensation product re sulting from the process be heat-stable; and followed by neutralization with gluconic acid.

3. A two-step manufacturing process including the method of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity;

said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunction-a1 phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (0). formaldehyde; said condensation reaction being conducted. at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conductedso as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the .amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximateiy l, 2 and 2 respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable; and followed by neutralization with gluconic acid.

4. A two-step manufacturing process including the method of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said-resin being derived by reaction between a difunctio-nal monohydric phenol and fcrmaldel'iyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable; and followed by neutralization with gluconic acid.

5. A two-step manufacturing process including the method of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant 5 portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehydederived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable; and followed by neutralization with gluconic acid.

6. A two-step manufacturing process including the method of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, waterinsoluble, low-stage phenol-formaldehyde resin having an average molecular Weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2, 4, 6 position; (b) a basic hydroxylated secondary monoamine having not more than 32 carbon atoms in any group attached to the amino nitrogen atom, and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; with the added provision that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable; followed by neutralization with gluconic acid.

7. The method of claim 6 where R is substituted in the para position.

8. The product resulting from the process defined in claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 1,996,069 Honel Apr. 2, 1935 2,031,557 Bruson Feb. 18, 1936 2,499,365 De Groote Mar. 7, 1950 

1. A TWO-STEP MANUFACTURING PROCESS INCLUDING THE METHOD OF CONDENSING (A) AN OXYLKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATERINSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 